JPS58215434A - Forming composition based on polymer reinforced with mineral filler, manufacture, means for carrying out same and formed articles therefrom - Google Patents

Abstract

Molding compositions for the fabrication of shaped articles having enhanced mechanical properties are comprised of (i) a polymeric matrix, (ii) an inorganic reinforcing filler material therefor, and, advantageously, (iii) a polymer/filler coupling agent, said reinforcing filler material consisting essentially of intimate admixture of enstatite and silica advantageously prepared by calcination of a precursor clay at a temperature of at least 800 DEG C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to molding compositions consisting of a polymer and a mineral reinforcing filler, the mineral filler optionally bonded to the polymer by a coupling agent. More particularly, the present invention relates to compositions based on thermoplastic, thermosetting or elastomeric reinforcing polymers in which the mineral fillers have improved binding capacity. Furthermore, the invention relates to methods for producing these compositions, means for carrying out these methods, and molded articles obtained by molding these compositions.

It is well known in the prior art for polymers to contain non-polymeric materials as fillers in order to improve some of their properties. For example, the mechanical properties of the polymer, such as its coefficient of expansion and/or its abrasion resistance and/or its modulus of elasticity and/or its tensile I3! A and (
or) various mineral fillers can be used to specifically improve its flexural strength and/or its elasticity. The key to developing compositions of this type containing fillers is to establish an effective bond between the filler and the polymer.

Without this bond, the addition of fillers can interfere with the mechanical properties of the polymer species.

Establishing this effective bond involves changing the properties of the filler, which may require the use of a more or less effective coupling agent, that is, a compound that is reactive with both the polymer and the inorganic filler. It can be realized by The camping agent must have at least one group capable of reacting with the polymer and at least one other group capable of reacting with the functional group (usually the 01 group) present on the surface of the filler. No.

Various organosilicon compounds are used as coupling agents. Suitable compounds of this type are described, for example, in 7 Lance Patent No. 1.599.049, in which -ff is replaced by an alkoxysilane group -8i-OR (in the formula R represents a lower alkyl group] is generally contained.

Generally, not all mineral fillers are equally effective as reinforcing fillers. The necessary conditions for this effect are
There is a sufficient density of functional groups on the surface of the filler to react with the polymer and optionally the coupling agent. Many mineral fillers have been proposed, the most typical of which are of the following types: calcium carbonate, titanium oxide, micronized silica, aluminosilicate salts such as calcined kaolin, magnesium salts such as talc, etc. Silicate, wollastonite and calcium sulfate.

Experiments carried out by the applicant using 46 knife as polymer allowed it to be observed that calcined kaolin and talc are the vine fillers that give the best compromise in terms of mechanical properties. . In general, talc is preferable because it causes less shrinkage of the molded product.

By continuing research in this field, Applicants have discovered other effective fillers that may compromise mechanical properties better than previously reported.

Roughly in detail, the present invention provides a molding composition comprising: (a) a polymer; (a) a mineral reinforcing filler; and, if necessary, (C) a coupling agent, wherein the mineral filler is primarily The present invention relates to a molding composition characterized in that it consists of an intimate mixture of pyroxene and silica, such as those obtained by calcining a suitable type of clay at a temperature of at least 800°C.

Examples of suitable types of clay that may be mentioned are chlorite, illite, haligorskite, sabotite, talc or mixtures of these types.

The polymer reinforced according to the invention can be primarily a synthetic thermoplastic glass, which has a high number average molecular weight with a value of at least 2000 and which softens when exposed to sufficient heat. , and returns to its initial state when cooled to room temperature. These thermoplastics include, for example, polyolefins, polyvinyl chloride and its copolymers, polyamides, saturated polyesters,
Includes polycarbonate as well as thermoplastic polyurethane.

Preferred types of thermosetting polymers that can be used in this invention include polyolefins, polyamides and polycarbonates. Examples of typical types of polyolefins are high and low density polyethylene, polyglobylene and ethylene/propylene copolymers. The term "polyamide" is understood to mean products obtained primarily by polycondensation of diacids with diamines or by homopolymerization of amino acids or by polymerization of lactams. Typical examples of this type of polyamide are nylon 6.6 (a polymer of hexamethylene diamine and adipic acid), nylon 410 (a polymer of hexamethylene diamine and sebacic acid), and nylon 6 (a polymer of -monocaglolactam). polymer), 7 nylon (polymer of aminononanoic acid), ? These include nylon (a polymer of aminononanoic acid), nylon 11 (a polymer of ω-amino-undecanoic acid), mixtures of these polymers, and copolymers obtained from the above monomers. The term "polycarbonate" is understood to mean primarily the products resulting from the reaction of dihydrexylated aromatic compounds, in which the hydroxyl groups are bonded directly to the aromatic nucleus, with carbonic acid. A particularly representative example is poly-(bisphenol A) carbonate.

The polymer reinforced according to the invention is, secondly, a synthetic thermoset, which under the action of heat begins to soften (if it has not already softened) and then gradually hardens into a solid phase. and this solid state will last indefinitely. These thermosetting materials include, for example, phenolic resins, ζ-unsaturated polyesters, epoxy resins, polyimides, and crosslinked polyurethanes.

Preferred types of thermosetting polymers that can be used in the present invention consist of phenolic resins and polyimides. “pheno-
The term "resin" is understood to mean a product obtained primarily by polycondensation of an aldehyde with a 7-enol. Examples of typical types of heptenolic resins of this type are condensates of phenol, resorcinol, cresol or xylenol with formaldehyde or furfural.

The term "polyimide" is understood to mean the product obtained by reacting primarily an unsaturated dicarboxylic acid, N,N'-bis-imide, with a primary polyamine. Products of this type are described in French Patent No. 1.555,564,
U.S. Patent Nos. 4562,225 and 4658.764
No. 29,516 and US Patent Reissue No. 29,516. A particularly representative example is the product obtained by reacting N,N-4,4-phenylmethane-pisumaleimide with 4,4-diaminodiphenylmethane.

The polymers reinforced according to the invention can thirdly - be natural or synthetic elastomeric materials. These materials include, for example, natural rubber, homopolymers of conjugated dienes such as butadiene and isoprene, ethylenic and
or) copolymers obtained from vinyl aromatic halfcaps and conjugated dienes, such as styrene/butadiene copolymers, isobutylene/isoprene copolymers (butyl rubber) and ethylene/propylene/hexa-1,4-diene copolymers. butadiene/acrylonitrile copolymers, halogenated rubbers such as chlorinated natural rubber, brominated and chlorinated butyl rubbers and polytetraprenes, elastomeric polyurethanes,
Includes polysulfides as well as elastomeric silicones.

Preferred types of elastomeric polymers that can be used in the present invention are polychloroprene and elastomeric silicone colors. The term "elastomeric silicone" is understood to mean primarily products obtained by crosslinking polysiloxanes having alkyl, alkenyl, Schiffrealkyl, phenyl and/or hydroxyl groups under the action of heat. A particularly representative example is a dimethyl borosilicate xane elastomer having a small proportion of vinyl groups.

Of the various polymers described above, polyamides are particularly suitable for curing according to the present invention.

Nylon 46 and Nylon 6 and mixtures thereof are very particularly suitable.

The mineral-reinforced filler according to the invention consists of a suitable clay that has been subjected to a calcining process. This treatment consists of heating the selected mineral to a temperature of at least 800°C;
This step is carried out in the air, under a nitrogen atmosphere, or under a humid air atmosphere. The process can be carried out in a static oven or in a rotary oven or in a flash firing apparatus.

This calcination, on the one hand, causes a dehydroxylation reaction of the mineral, causing it to lose its structural water above 800°C, and, on the other hand, a transformation reaction of its initial crystal structure, resulting in the formation of pyroxene and amorphous silica. This results in an intimate mixture with silica in the form of crystalline silica in the form and/or in the chrysoparite state. Traditionally, mineral fillers have been said to "consist primarily" of an intimate mixture of pyroxene and silica, and the expression "predominantly" means that the fired mixture contains roughly small amounts of mineral impurities that are related to the nature of the deposits. This does not constitute a problem for the present invention. The heating time is not critical and can vary over a wide range, for example from a fraction of a second (for flash firing) to about 10 hours (
(in the case of standing still or firing in a rotary furnace). Of course, this time must be sufficient in all cases to carry out the crystallographic transformations described above.

The mineral-reinforced filling suitably used to carry out the present invention can be used at m
It is baked by heating at a temperature of 2 to 5 hours or made of talc.

It should be noted that the use of this talc to strengthen polyamides represents a particularly advantageous embodiment of the invention.

The particle size of the reinforcing filler can vary, and this is not a particularly critical property. Usually α1 miku pun~100
Fillers containing particles having dimensions of microns, preferably from 15 microns to 50 microns, are used. The specific surface area of the particles is not a particularly critical variable and is usually between 1 and 25 m
t/f/, preferably 2 to 15 m"/l!

The amount of mineral reinforcing filler to be used to produce the compositions according to the invention can vary within a wide range. The maximum percentage is primarily limited by the polymer's ability to bind the reinforcing filler into a cohesive material. Typically, this maximum percentage is about 9% based on the total weight of polymer and mineral reinforcing filler.
It is a zero-fold foot arc. The minimum proportion corresponds to the amount of filler necessary to begin to see an improvement in the mechanical properties of the polymer. Typically, this minimum proportion is about 2% by weight based on the total weight of polymer and mineral reinforcing filler. The proportion of vine reinforcing filler used therefore ranges from 2 to 90%, preferably these ranges from 10 to 60%.

Furthermore, the compositions according to the invention can also contain coupling agents, which is a particularly advantageous measure. usually,
This coupling agent is selected from the polyfunctional organosilicon compounds mentioned at the beginning of this specification. These compounds contain at least one other group capable of bonding to the mineral filler. The nature of said other functional groups will, of course, depend on the polymer used. For example, coupling agents containing vinyl groups are compounds that can be used with e.g. polyolefins and thermoset polyesters; examples of suitable organosilicon compounds are vinyltrimethoxysilane, vinyltrinidoxysilane and vinyltri(2-methoxysilane). mercury) - silane.

Camping agents with acrylic or methacrylic groups are vine compounds used with polyolefins and thermosetting polyesters, examples of suitable organosilicon X compounds are r-
It is methacryloxygosepyrtrimethoxysilane.

Ami7 coupling agents include, for example, polyvinyl chloride, polyamide, thermoplastic polyester, polycarbonate, thermoplastic polyurethane, phenolic resin, epoxy resin,
Examples of suitable organosilicon compounds include r-aminopropyltriethoxysilane, r-aminopropyltriethoxysilane and N
-(β-aminoethyl)-r-aminopropyltrimethoxysilane. Epoxidized coupling agents are compounds that can be used with generally thermoplastic polyesters, phenolic resins and epoxy resins; examples of suitable organosilicon compounds are β-(44-epoxysilane)-ethyltrimethoxysilane and r -Glycid-oxypropyltrimethoxysilane. Coupling agents containing mercapto groups are, for example, phosphor compounds used with polychloroprene; examples of suitable organosilicon compounds are r
-Mercaptoglobiltrimethoxysilane.

Acidosilanes (or silanesulfonyl azides) are also suitable as coupling agents. Compounds of this type have been described by G.N. Mactuaren et al. in Polymer Engineering and Science, (1977), Vol. 17,
No. 1, pages 46-49, r2.

The amount of coupling agent required to ensure good bonding between the mineral reinforcing filler and the base polymer is relatively small. Using a coupling agent in an amount of only α1% by weight relative to filler overlay, it is possible to produce compositions with superior mechanical properties compared to compositions containing untreated fillers. can.

Typically, amounts of coupling agent (13% to 4%) have been found to be very satisfactory. It was discovered this month that higher amounts can be used without compromising the properties of the final product. be.

The reinforced polymeric composition according to the invention can be produced in various ways known per se.

Starting from thermoplastic and thermosetting polymers, the various components are preferably mixed in two stages. That is, in the first step, the various ingredients are stirred at room temperature in a conventional powder mixer (which can simply be the feed hopper of an extruder);
In a second stage, the mixture is homogenized by hot kneading in a single-screw or multi-screw extruder. After this treatment, the composition of the invention generally takes the form of a rod, which is then cut into granules.

These granules are then used to form the desired articles in conventional injection ffi, transfer molding or extrusion equipment.

When starting with an elastomeric polymer, all of the various components are generally placed directly into a mixer heated to an appropriate temperature, such as a suitable slow mixer (slow mill, internal mixer, kneading seal, etc.). These various components are mixed by introducing them. After this treatment, the compositions of the invention are generally in the form of pastes of various thicknesses, and these pastes are then used to form the materials as desired by conventional techniques for shaping elastomeric materials, such as by calendering or by molding. Shaping the composition. After shaping the compositions as desired, they are subjected to a hot-flow treatment.

If it is appropriate to use a coupling agent, this coupling agent can be incorporated into the medium for preparing the composition according to the invention in various ways. In the first method, the coupling agent can be pre-attached to the filler used to strengthen the polymer, and in the second method, the coupling agent can be pre-attached to the polymer before adding the filler. In a third method, the coupling agent can be mixed directly with the polymer and filler. Taking into account the above, the expression "various components" mentioned above in connection with the method for producing the composition according to the invention means: Method 1: Pre-treated mineral filler and polymer preparation Method 2: Mineral filling Agents and Pretreatment Polymer Placement Method 5: Polymer, Mineral Filler, and Coupling Agent.

If a coupling agent is used, the treatment with it is generally by incorporating it directly or gradually in the pure state, or into fillers (Method 1) or into polymers (Method 2) in a suitable solvent. , into a mixture of filler and polymer (method 3)
) dissolve. Particularly in the case of method 1, the filler can be processed by the technique of fluidized bed mixing or by the technique using a rapid mixer.

In general, the polymeric composition according to the invention is prepared by preparing a master mixture supplied in the form of granules or pastes based on part of the polymer to be reinforced, fillers and optionally coupling agents, and then this can be prepared by mixing with the remaining granules or paste of the polymer to be strengthened before processing.

Another method for producing the composition according to the invention consists in polymerizing the monomers forming the polymer in the presence of a suitably treated reinforcing filler, in which case the polymerization is carried out in the form of a polymer having the shape of the desired article. It can be done in a mold. Treatment with a coupling agent can be carried out during the polymerization if this treatment is used.

Furthermore, the polymeric composition according to the invention may contain one or more additives, such as pigments, stabilizers, nucleating agents, curing agents, vulcanization accelerators, rheology properties modifiers as well as improving the surface finish of the article. It may also contain compounds or compounds which modify the properties of the composition upon shaping. The amount of these additives incorporated generally does not exceed 40% of the weight of the polymer matrix.

Starting from polyamides, which are particularly suitable polymers for carrying out the invention, at least one olefin and at least one other copolymerizable monomer having carboxyl and/or carboxylic acid groups are used. A polymer compound consisting of a copolymer obtained from and can also be mixed into the compound of the present invention to further improve the mechanical properties at low temperatures in the range of 0°C to -20°C.

More particularly, the following can be used in this sense: aliphatic α-olefins with 2 to 6 carbon atoms (e.g. ethylene, propylene, butene-1, pentene-1)
1 or hexene-1) and an α,β-unsaturated monocarboxylic or dicarboxylic acid having 3 to 8 carbon atoms (
acrylic acid, methacrylic acid, maleic acid, heptamalic acid, itaconic acid or vinylbenzoic acid) and at least one compound belonging to the class consisting of the lower alkyl esters and anhydrides obtained from these acids. system copolymer. Examples of suitable copolymers are ethylene/acrylic acid, ethylene/methacrylic acid and ethylene/acrylic! / methyl methacrylate copolymer; contains a carboxyl group and/or a carboxylic acid group, and has at least one ethylene and 3 to 6 carbon atoms.
An olefin copolymer derived from α-olefin of species. Propylene is preferably used as α-olefin having 3 to 6 carbon atoms, but other α-olefins of this type
-Olefins, in particular butene-1, pentene-1 or hexene-1, can also be selected instead of or in addition to propylene. carboxyl group and/or
The introduction of carboxylic acid groups is carried out using ethylene/α-olefins with 3 to 6 carbon atoms and α,β-unsaturated dicarboxylic acids with 4 to 8 carbon atoms (maleic acid, fumaric acid or itaconic acid). and by direct copolymerization of a mixture with at least one unsaturated compound belonging to the class consisting of lower alkyl esters and anhydrides obtained from these acids, or by direct copolymerization of a mixture of acidic compounds (acid and/or rust conductor) on the olefin base. This can be carried out by grafting, which is followed by ionization or hydroperoxidation or under the action of heat and pressure. Examples of suitable copolymers are copolymers of maleic anhydride grafted to ethylene/propylene and copolymers of fumaric acid grafted to ethylene/propylene: and containing ethylene and at least one having 3 to 6 carbon atoms
A copolymer composed of an α-olefin and at least one non-conjugated diene.

Here too, preference is given to using propylene as alpha-olefin having 6 to 6 carbon atoms.

Non-conjugated dienes usually consist of aliphatic dienes having at least 6 carbon atoms, which have terminal double bonds and internal double bonds, hexa-14-diene being preferably used. The introduction of carboxyl groups and/or carboxylic acid groups is carried out by treating the ethylene/α-olefin/diene mixture in the same manner as described above for the ethylene/α-olefin mixture. Examples of suitable copolymers are copolymers of maleic anhydride grafted on ethylene/propylene/hexa-14-diene and copolymers of fumaric acid grafted on ethylene/propylene/hexa-1,4-diene. It is a combination.

Copolymers with functional groups belonging to the above-mentioned class have already been used for reinforcing polyamides.

For details regarding their definition and the conditions of their use, reference may be made to French Patent No. 2,511,814. The amount of optional functionalized copolymer with groups generally ranges from 2 to 60% based on the weight of the basic polyamide of the composition.

The compositions according to the invention are characterized by mechanical properties not obtainable with conventional mineral-reinforced polymers, especially polyamides. More specifically, 4300MP
A flexural modulus greater than a (measured under the conditions described below) and 5
KJ/I! "Notch impact strength greater than
A filler-containing giriamide can be produced that has a 100% polyamide (as measured under the conditions described below). Conventional polyamide composition containing talc (uncalcined) as filler 600
They have flexural moduli that can reach or exceed 0 MPa, but these are generally up to 4 KJ/m! It has a notch impact strength of For polyamide compositions containing calcined kaolin as a filler, they generally have satisfactory notch impact strengths;
It has a flexural modulus lower than the value of a and a thermal strain point under load lower than 85°C.

The following examples illustrate how to implement the invention.

Example 1 The following were brought into direct contact with each other in a lawn mixer from Engelsmann: 46 Naon 5500jJ' marketed by P-Noop-Lan Specialité Simique as Chikuel 216 (W-Registered Trademark) 1500 g of talc, marketed by Société des Talcs de Luzenac, calcined for 4 hours in a static oven at a temperature of 1000'C; the particle size distribution of this filler is as follows: particles smaller than 20μ 100%, 1
90% particles smaller than 0μ, 60% particles smaller than 5μ
, and 20% of particles smaller than 2μ; their specific surface area is about 5
wt”/f.

r-Aminopropyltriethoxysilane 159°, commercially available as Silane A110D® by Union Carbide. This mixture was homogenized at room temperature and then
The mineral filler was dispersed into the polyamide matrix by introducing it into the feed holator of a double-screw extruder of the type P7Lider® ZSK50. The temperature distribution of the extrudate was equilibrated under uniform operating conditions as follows: inlet: 262°C; middle of extruder body = 270°C; end: 272°C; die: 270°C.

The rotational speed of the screw was fixed at 200 rpm. The output rate of the extruded product was on the order of 114 k) 7 hours. The extruder was fitted with a die with three holes to obtain a bar which was then approximately 5 mm long and 15 mm in diameter.
cut into granules.

In order to test the mechanical properties of the articles obtained from these granules, a number of tests were carried out, the properties of which are shown below: Flexural test: flexural strength and flexural modulus were determined according to ASTM Standard Method D
790 and the heat strain temperature under load (HDTL) is measured as specified in ASTM standard method D64B; Charpy impact V test: Charpy impact strength on notched specimens is measured as specified in EH AS using the conditioned specimen
Measure as described in TM standard method D256 (specimen placed in a desiccator on silica gel, α67
Measurements are taken after drying again for 24 hours under reduced pressure between X10" and t33x10" PH).

To prepare the specimens necessary to conduct these tests, these granules were mixed with Pula-Roper® 100
A molded product was produced by introducing the molded product into a B-type injection molding apparatus. This mold is a "finger" type, and each finger is the Af
Corresponds to a test piece whose shape and dimensions correspond to those specified by the fTM standard method. In this apparatus, the granular molding composition was melted at a temperature of 270<0>C to 280<0>C, while the mold was maintained at a temperature of 60<0>C. The injection pressure was 750×10' Pa. The time for one injection cycle was 30 seconds. The results of the bending test and impact test are shown in Table 1 below.

As a comparative test (test person), the same operation as above was repeated, but in this case uncalcined talc was used.

Furthermore, as a comparative test (Test B), the same operation as above was repeated, but in this case calcined talc 1500I! Instead, an equal amount of calcined kaolin, sold by English China Clay Company as Polestar® 200R, was used. The particle size distribution of this filler is as follows: 999% particles smaller than 50μ; 1o
95% particles smaller than μ and 60% particles smaller than 2μ
; Its specific surface area is approximately 8.5 mK''/p.

Table 1 The molded article containing calcined talc (Example 1) has a more pale beige color, which is preferable to the gray color of the article containing uncalcined talc (tester). The article containing calcined kaolin (Test B) has a fairly dark beige color.

Example 2 The same operation as described above in Example 1 was repeated, but in this case 15
In place of the 00J calcined talc, the same amount of palygorseite calcined at 850°C for 4 hours was used. This type of clay was obtained from Renouboulin-Simy-de-Baze's Bort-aux-Senegales-Debositos. The particle size distribution of this filler is as follows: particles smaller than 50μ ion≦; 95% particles smaller than 20μ, 90% particles smaller than 10μ, 80% particles smaller than 5μ, and 2
70% of particles smaller than μ; their specific surface area is approximately 9/I.

The mechanical properties of the molded article obtained are as follows: Bending test: Strength: 133 MPa Elastic modulus: 41
15MP! HDTL Near 7°C Charpy Notch Impact Strength: 6 KJ/T0 Example 3 The following were brought into direct contact with each other for 6 minutes at room temperature in a Henschel rapid mixer rotating at 150 Orpm: As described above in Example 1 calcined talc 1500.9, which is the same as , and vinyltriethoxysilane 15, commercially available from Union Carbide Company as Silane A151 (registered trademark).
The mineral-reinforced filler thus obtained to which the I0 coupling agent was attached was treated with 5 sooy Napril 61400λG
The mixture was introduced into a lawn mixer containing polypropylene sold by British Petroleum under the trademark ®.

After stirring the whole at room temperature, the resulting mixture was homogenized by hot kneading in the Werner-Pfriederer extruder used in Example 1. The temperature distribution is as follows: Inlet = 240°C; Center of extruder body: 250°C; End: 230°C: Die: 230°C.

The rotation speed of the screw was fixed at 200 rpm,
The production rate of the extruded product was about 12 to 17 hours.

The bars obtained were granulated and the granules were then subjected to a molding operation using the injection molding apparatus described above in Example 1. In this apparatus, the granules were melted at a temperature of the order of 240<0>C to 250<0>C, while the mold was kept at 45<0>C. Injection pressure is 75
[1×10'PJl.

The injection cycle time was 25 seconds. The results of the bending test and impact test are shown in Table 2 below.

As a comparative test (Test C), the same procedure as above was repeated, but in this case, instead of the 1500 F calcined talc, the same amount of calcined kaolin marketed as Whitetex® by Freeboard Kaolin Company was used. did.

The particle size distribution of this filler is as follows: 99.9% particles smaller than 10μ; particle size 9 smaller than 5μ.
0%; and 60% particle size smaller than 2μ; its specific surface area is about 101/g.

Example 4 The same procedure as described above in Example 1 was repeated, but in this case poly-(bisphenol), commercially available as Lexan 101® by General Electric Company
Carbonate 3500.9 was used.

The yyv carbonate/calcined talc/silane mixture was extruded under the following temperature conditions: Extruder inlet: 280°C: Center of extruder body: 285°C; End: 290°C: Die: 300°C.

The rotational speed of the screw is fixed at 200 rpm, and the output rate of the extruded product is on the order of 1 sky/hour.

The resulting granules were molded using the injection molding apparatus described above under the following conditions: Material temperature: 305°C to 520°C; Mold +
7) I degree 85℃; Injection pressure 750X105Pa; Injection cycle: 60 seconds. The results of the bending and impact tests are shown in Table 6 below.

As a comparative test (Test D), Example 4 was repeated but':
, ノ′ζ.

In this case j5DD1! The same amount of uncalcined talc was used in place of the calcined talc.

1500 g of a powdered phenol/formaldehyde polycondensate of the /borac type having a melting point of near 9° C. and an apparent viscosity of 17 Pa, s at 132° C. in direct contact with each other in a p-simixer: Example: Calcined talc 1 obtained from the preliminary treatment carried out as shown in 3.
500 IC (same as described in Example 1) and 15 g of T-aminopropyltriethoxysilane; 49 oy of wood sawdust; 2'5 oy of hexamethylenetetramine; 201 oy of alkaline earth metal hydroxide! After stirring at room temperature 3 g of zinc stearate and 0.511° of a black dye marketed by Phenol Schwarz L (W®) and Lr Bayer, the resulting mixture was mixed with Wernabe 7 used in Example 1. Homogenization was carried out by hot kneading in a Leidera extruder. The temperature distribution is as follows: extruder inlet: 25°C; center of extruder body: 45°C; end: 105°C; die: 105°C.

The rotational speed of the screw is fixed at 2 D Orpm, and the production rate of the extruded product is on the order of 1 sky/hour.

The product coming from the extruder is ground into a powder, which is first heated at 90°C for 30 minutes and then operated at a temperature of 165°C and a pressure of 400 x 10'Pa. Dimensions 120 x 120 depending on the device
It was compression molded in the form of X 4 *yn platelets for 55 minutes. Test specimens, shapes and dimensions corresponding to the ASTM standard method described above in Example 1 were then cut from these plates. The results of the bending and impact tests are shown in Table 4 below.

As a comparative test (Test E), Example 5 was repeated, but in this case the same amount of uncalcined talc was used instead of 15 DOJi' of calcined talc.

The following components were brought into direct contact with each other in an internal mixer of the Panbari type from 7 Allele Company: Chloroprene ID0O!, marketed by Dystugil Company as Butachlor MC50®. i; Magnesha 40F, marketed by Merck & Co. as Magray) D (registered trademark) and Permanax OD (
Antioxidant Additive 20I!, marketed by Prunax, Inc. as a registered trade mark). .

After 5 minutes of stirring, the following were introduced into the mixer: 9
Talc 6001/ calcined for 4 hours in a static oven at a temperature of 50° C. and γ-mercaptopropyltrimethoxysilane 18I, marketed by Union Carbide as Silane A189®! The calcined talc used has the following particle size distribution: 100% particles smaller than 20μ: 80% particles smaller than 10μ; 55% of particles smaller than 5μ and 15% particles smaller than 2μ; its specific surface area is 411L! /Ii; and 100 g of a plasticizing additive marketed by Shell as Somil B®.

All the above ingredients were mixed for 12 minutes at a temperature on the order of 70°C.

The resulting cake was transferred to a Lv-type kneading roll from Brehre and kneaded for a further 12 minutes at room temperature in the presence of the following additional ingredients: Zinc oxide 501; Du Bont as NA22® Ethylene 1,000 urea 10 I, marketed by De Nimoas, and 5 g of tetramethylthiuram disulfide, marketed by Prunax, as Bulkahor/l/TMDT®.

The final mixture was heated to 160°C and 250×1Q.
” Vulcanized in a Vignette Emidekau compression molding apparatus in a mold operating for 12 minutes under the pressure of PR. Specimens of shape and dimensions corresponding to the standard method governing the mechanical tests performed were then cut. The tests carried out were as follows: Tensile test: Final 5 [Tensile strength and modulus at 200% elongation were measured as indicated by French standard method T46002; Tensile test: Tear strength was determined according to French standard method T46007 (Method C)
; Measurement of residual deformation after compression for 24 hours at 70°C (RD
C): This is carried out as indicated by the French standard method T46011; the determination of the abrasion resistance is carried out by the Tabick method. The results of the mechanical tests conducted are shown in Table 5 below.

As a comparative test (Test F), Example 6 was repeated, but in this case the calcined talc of 6001 was replaced with the same amount of uncalcined talc.

Example 7 The following components were brought into direct contact with each other in a rolling mill from Trostar: 60Q, 0 (polydimethylsiloxane 100# having a molecular weight of 10 and 16 vinyl groups per molecule; and The same calcined talc 40I!

After 15 minutes of kneading at room temperature, t211 of 2,4-dichlorobenzoyl peroxide was introduced into the resulting mixture and kneading was continued for a further 5 minutes.

The base sheet thus obtained was heated at a temperature of 115°C and
Vulcanization was carried out in a Binettier main Decau compression molding apparatus in a mold operating for 8 minutes under a pressure of 50.times.10" Pa. Specimens were then cut with shapes and dimensions corresponding to the standard method governing the mechanical tests performed. The tests carried out were as follows: Tensile test: Ultimate tensile strength and elongation at break were determined as indicated by the French standard method T4tSOO2; Measurement of tear strength: This was determined according to the ASTM standard method D6
24 at 177°C;
Measurement of compressive residual deformation (RDC) after 2 hours: This is AS
It was performed as indicated by TM standard method D395B.

The results of the mechanical tests conducted are shown in Table 6 below.

As a comparison (Test G), Example 7 was repeated, but in this case 4
0J of calcined talc was replaced with the same amount of uncalcined talc.

Claims (9)

[Claims] (1) In a molding composition comprising (a) a polymer, a) a mineral reinforcing filler, and, if necessary, a kaglinda agent, the mineral filler mainly contains a suitable type of clay. For molding, characterized in that it consists of an intimate mixture of pyroxene and silica, obtained by firing at a temperature of at least 800°C. (2) The types of clay used for firing are chlorite, illite,
9. Composition according to claim 8, characterized in that it is selected from the group consisting of palygorskite, sapoite, talc or mixtures of these types. (3) The composition according to claim H, item 2e, characterized in that talc is used. (4) The composition according to any one of claims 1 to 3, wherein the polymer to be reinforced is a thermosetting polymer. (5) The composition according to claim 4, wherein the polymer is polyolein. (6) A composition described in the patent claim Fllll, H*4TJi, characterized in that the polymer is polyamide. (7) The composition according to claim 4, wherein the polymer is polycarbonate. (8) The composition according to any one of claims 1 to 3, wherein the polymer to be reinforced is a thermosetting polymer. (9) The composition according to claim 8, wherein the polymer is a phenolic resin. 9. The composition according to claim 8, wherein the al polymer is polyimide. 0υ Composition according to any one of claims 1 to 3, characterized in that the polymer to be reinforced is an enstomer polymer. 03. The composition according to claim 11, characterized in that the polymer is borik pO prene. 03 The composition according to claim 11, characterized in that the polymer is an elastomeric silicone. Claims 1 to 13, characterized in that the compound is a polyfunctional organosilicon compound having a flufukidisilane group and at least one group bonded to a polymer. Composition. OQ 2 for the total weight of polymer and mineral reinforcing filler
a mineral reinforcing filler in a proportion of ~90 wt-1, preferably 10 to 60 wt.%, and, if a coupling agent is used, a coupling agent in a proportion of C13 to 4 ff1% relative to the weight of the mineral reinforcing filler; The composition according to any one of claims 1 to 14, characterized in that it contains the following. aQ Starting from a thermosetting polymer or a thermosetting polymer, the various components are mixed in two stages, in the first stage the various components are stirred in a conventional powder mixer at room temperature,
Claims 1 to 10, characterized in that in the second step, this mixture is homogenized by hot mixing in a single screw or multi-screw extruder.
14. A method for producing a composition according to any one of Items 14 and 15. Starting from an αη elastomer polymer, the various components are mixed by introducing them all directly into a suitable slow mixer heated to a suitable temperature. A method for producing a composition according to any one of items 3 to 3 and items 11 to 15. α Barrel Patented to which a coupling agent made of a polyfunctional organic silicate compound having at least one alkoxysilane group capable of bonding to a mineral filler and at least one group capable of bonding to a polymer is attached in advance. 18. A method according to claim 16 or 17, characterized in that it involves the use of a mineral reinforcing filler according to any of claims 1 to 3.